Polyaniline reactions

The stoichiometry of the redox reactions of conducting polymers (n and m in reactions 1 and 2) is quite variable. Under the most widely used conditions, polypyrroles and polythiophenes can be reversibly oxidized to a level of one hole per ca. 3 monomer units (i.e., a degree of oxidation, n, of ca. 0.3).7 However, this limit is dictated by the stability of the oxidized film under the conditions employed (Section V). With particularly dry and unreactive solvents, degrees of oxidation of 0.5 can be reversibly attained,37 and for poly-(4,4 -dimethoxybithiophene), a value of n = 1 has been reported.38 Although much fewer data are available for n-doping, it appears to involve similar stoichiometries [i.e., m in Eq. (2) is typically ca. 0.3].34,39"41 Polyanilines can in principle be reversibly p-doped to one... 

Fig. 5.34 Schematic representation of the oxidation/reduction and acidobasic reactions or polyaniline...

The electrochemistry of polyaniline is more complex than that of other conducting polymers and given the large number of possible structures for the material, it is not surprising that many possible reaction schemes have been suggested [181,182, 195-197,205], Many of the properties of the material are pH-dependent [173,174, 206], including the open circuit potential [207] which is most positive at pH 0, and this is further complicated by the fact that not all the polymer chains are necessarily in exactly the same state at any given time [197]. Above pH 3 polyaniline films do not show any electroactivity, but are not electroactive even at low pH with... 

Kobayashi T., Yoneyama H., Tamura H. Electrochemical reactions concerned with electrochromism of polyaniline film-coated electrodes. J.Electroanal.Chem 1984 177 281-91... 

Polyaniline (PANI) was investigated as electrocatalyst for the oxygen reduction reaction in the acidic and neutral solutions. Galvanostatic discharge tests and cyclic voltammetry of catalytic electrodes based on polyaniline in oxygen-saturated electrolytes indicate that polyaniline catalyzes two-electron reduction of molecular oxygen to H2O2 and HO2". 

Y.-Q. Miao and J.-G. Guan, Probing of antibody-antigen reactions at electropolymerized polyaniline immunosensors using impedance spectroscopy. Anal. Lett. 37, 1053—1062 (2004). 

The polymer resulting from oxidation of 3,5-dimethyl aniline with palladium was also studied by transmission electron microscopy (Mallick et al. 2005). As it turned out, the polymer was formed in nanofibers. During oxidative polymerization, palladium ions were reduced and formed palladium metal. The generated metal was uniformly dispersed between the polymer nanofibers as nanoparticles of 2 mm size. So, Mallick et al. (2005) achieved a polymer- metal intimate composite material. This work should be juxtaposed to an observation by Newman and Blanchard (2006) that reaction between 4-aminophenol and hydrogen tetrachloroaurate leads to polyaniline (bearing hydroxyl groups) and metallic gold as nanoparticles. Such metal nanoparticles can well be of importance in the field of sensors, catalysis, and electronics with improved performance. 

Note 1 Reversible redox reaction can take place in a polymer main-chain, as in the case of polyaniline and quinone/hydroquinone polymers, or on side-groups, as in the case of a polymer carrying ferrocene side-groups. 

Kraft et al., 1998 Lowen and Van Dyke, 1990 Wei and Tian, 1993], Reactions other than oxidative polymerization are also being studied for producing polyaniline and polythiophene [Kraft et al., 1998 Loewe et al., 2001]. An example is the Pd-catalyzed dehydrohalogenation between aryl dihalides and aryl primary diamines to synthesize polyanilines [Kanbara et al.,... 

Several phosphines, such as 2,4,4-trimethylpentylphosphine and phenylphosphine, give similarly the corresponding polymers. Several phosphorous-containing polyanilines are also prepared in a similar manner by the palladium-catalyzed polycondensation reaction. 

---